Azo dyes insoluble in water and process of making same



Patented Atig l9, EQEQ,

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nu-cuss macaroni) Lesm Ann An'rnnn zrrscnnn, or orrnnBacn-on-rnE-nam, ennnrnnr, nssrenons are THE conrom'rron or cnnmscnn nanamenmsnmnannrnon, onrnanxronr-on-rnn-nnm, GERMANY. I I y 7 A20 DYES IN SOLUBLE HQ WATER. AND PROCESS OF A ?I: G SAME. I 7

No Drawing.

To all whom it mdypomem:

Be it known that we, AUGUST Lnorom) LAsKA and ARTHUR Zrrsomin, both citizens in Azo Dyes Insoluble. in Water and Proc-' esses of Making Same; and we do hereby; declare the following to be a ifull, clear, and exact description of the invention, such as will enable others skilled in the art to which it appertains to make and use the same.

Our invention relates to new azo dyestufi's, which can be used for the production of pigment colors and which can be also produced on the vegetable fibre.

We have found,"that by combining a diazo compound n-ot containin a sulfo or carboxylic group with a diacy acetyl compound of the benzidine series of the general formula:

Y.CG.CH .OO.Nl-I.X.NH.OO.CH .CO.Y,

wherein X means a diaryl residue, Y any radical "of the hydrocarbon series, azodyestufis, insoluble in water, are obtained, which are distin ished by valuable properties. 7

Under t e term any radical of the hydrocarbon series, for Y we include as well ali hatic as, aromatic radicals.

have found, sufliciently colored pigments areobtained not only. by the combinations of nitrodiazo compounds with the diacylacetyl com ounds of the benzidine series but also by t e combinationof diazo com ounds of chlorine substituted anilines an even of cm-coom-cd-Nn and its. derivatives, substituted the dighenyl residuekdibenzoylacetyl benzidine, its:

as can be produced by condensing acylacetic erivative's, 'su stituted in the diphenyl resi' due, and other diarylacetyl compounds, which Application filed November 23, 1922. Serial no. ceases.

anilineitself and of its homologues with diacylacetyl compounds of the benzidine series. 1

Especially surprising and important is the discovery, that the diacylacetyl compounds of the benzidine series possess a certain affinity for cotton makin possible the production of the dyestu s on the fiber by padding the material with an alkaline solution of a diacylacetyl compound of the benzidine series and after squeezing without drying, developing with a diazo compound. The colors thus obtained arecompletely fast to washing, they show a good, partly extraordinary fastness to li ht and an excellent fastness to chlorine. y using the known combinations with the aceto-acetic-acid arylides it was hitherto not possible, to produce sufliciently strong and useful colors on cottoili yarn by means of the process for ice co ors.

' The new dyestufi's are, when dry, yellow to brown and Bordeaux red powders, insoluble in water, and soluble in sulfuric acid to a yellow to violet solution, giving, mixed with substrate, usual for the production of color lakes or produced in their presence valuable pigments, the fastness to oil being conditional'upon the nature of the substituents in the diazo .or arylamine residue and dyeing, when produced on the fiber, cotton in fast yellow to brown and Bordeaux red shades.

As diazocompoundswe may use in this process thoseof aniline and its homologues and substitution products, such as toluidines,

anisidines, chloroand nitroanilines, chloroand n trotoluidlnes, chloroand mtroanisidines,, also those of naphthylamines,

aminoanthraquinones, aminoazo compouii'ds, diamlnobases and others, as azo components we may use diacetoacetyl-benzidine itself (its formula being Nn-cocm-cocm) acid esters with diamino bases of the diphenyl series. I

- 'The following examples illustrate the invention, the parts being byweight.

i K Example, 1.-

32.4: parts of 2.5-dichloroaniline are diazotized in the usual manner and the diazo solution is added to a solution of 40 parts of CHn-COCHg-CO-NH-i When the combination is complete, the dyestuff is filtered, well washed and ground to a paste. lWiXed with the usual substrata it forms a reddish yellow lake of a very good fastness.

Emample 2.

25.5 parts of ortho-chloroaniline are diazotized in the usual manner and the diazosolution is added to a solution of 4:9 parts of dibenzoylacetyl-benzidine in aqueous alkali, to which is added a sufiioient quantity'of sodium acetate. When the combination is complete, the dyestuff is filtered, well washed and ground to a paste. Mixed with 20 cc. of Turkey red oil in the liter, Well wrung out and after or without being dried, developed in a diaz'o solution, with an addition of sodium acetate and containing 2.8 gr. of 5'-chloro-1.2-toluidine or 2.6 gr. of ortho-chloroaniline or 2.8 gr. of ortho-nitroaniline in the liter.

In this manner we obtain greenish yellow tints with 5-chloro-12-toluidine, lemon yellow tints with ortho'chloroaniline and orange yellow tints with ortho-nitroaniline, all

' tints being of an excellent brightness and a good fastness.

Example 4.

The yarn having been well boiled and dried, is impregnated with a solution of 10 gr. of dibenzoylacetyl-ortho-tolidine 15 cc. of caustic. soda lye of 34 B. and

20 cc. of Turkey red oil in the liter, well wrung out and, without being dried, developed in a diazo solution, with an addition of sodium acetate and containing 2.8 of Q-chloro-L l-toluidine in the liter. In this manner, clear, reddish yellow tints of an excellent fastness are obtained.

The new dyestufi s can also be produced by printing a di-azo solution upon a padded fabric according to the usual method, also according to the method of nitrosamine printing.

diacetoacetyl-ortho-tolidine in aqueous alkali, to which is added a sufficient quantity of sodium acetate. The formula of diacetoa'cetyl-ortho-tolidine is With other diacetyl compounds of the benzidine series the process may be conducted similarly.

The following table gives some of the shades of a/number of-dyestuifs, prepared according to the present process, and of the Eolor lakes, respectively, obtained thererom:

Combined with Diazo compound from- Shades.

2.5-Dichloroaniline Dgiicetoncetyl-benzh Yellow.

Ortho-nitroaniline Reddish yellow. 4Chloro-2-nitroaniline Reddish orange yellow. 3-Nitro-L4-toluidine.. Brownly orange E-Nitro-LZ-toluidine. Orange yellow.

4-Nitro-L2-anisidine. Yellow. fi-Nitro-LZ-anisidiue do Brownly orange yellow 3-Nitro1A-anisidine do Reddish orange yellow. Ortho aminoazotoluene. do Brownly yellow. Di'misirline rln rown. Aniline Diacetoacetyl-ortho- Greenish yellow.

. tolidine.

Ortho-toluidine d Greenish yellow. Para-aminoacetanilide.-. Yello Ortho-aminophenylether Ortho-chl0roaniline w. Greenish yellow. Lemon yellow.

Meta-chloroamline D0. v Para-chloroaniline- Do. 2.5-Di chloroaniline D0.

Greenish yellow.

D". 4-Chloro-l.2-anisidine D0.

Lemon yellow. Orange yellow.

5-0 hloro-l .2-anisidine. O rtlio-nitroaniline.

4-Chloro-2-'nitroaniline. Reddish orange yellow. v

3-Nitrol.4-toluidine Orange yellow.

4-Nitro-l-naphthylamin Yellowish brown.

a.-A1ninoanthraquinone Brotylnly orange ye ow Brownish orange.

Yellowish orange. Yellow.

Orange.

Reddish orange. Reddish orange.

Orange red.

Brownish Bordeaux.

amine. Ortho-chlorobenzene-azoa-naphthylamine. 2:5-Dimethoxybenzeneazo-a-naphthylamine. Para methoxybenzenenzo-l amino 2-naphtholethylether. Para-aminobenzene-azodimethylaniline. 4.4 Diaminodiplienylamine.

Bluish Bordeaux.

Brownish orange.

Brown.

Para-aminobenzene-azo- Reddish brown.

a-naphthylamme. v Aniline Diacetoacetyl g. 0

Reddish yellow. dlchlorobenzi I Ortho-chloroaniline Do. 2.5-Dichior'oaniline Do. 4-Cl1loro-L2-anisid Do. 5-Ch1oro-L2-toluidine- Do. Ortho-nitroaniline Do. 4-Chloro-2-nitr Do. fi-Nitro-LZ-toluidine do Do.

Dlazo compound rome- Qombined witli' a-Aminoanthrequinone- Dlacetoacetyl-o.0!- Orange.

dighlorobenzidin- 1 e Ortho-amlnoazotoluene -..do Orange yellow. o.o -Dichlrobenzidmedo Bro yellow. Aniline Diacetoacetyl-dinn- Lemon yellow.

isidlnide. oytho-nhlm nnnilinn r n Yellow. 2.5-Dichlornanilinn r n Reddlsh yellow. -Chl010-L2-fnlnidlnn r n Lemon-yellow. 4-ChIoro1.2-anisidine o Reddish yellow. OrthO-nltrnaniline Orange yellow. e-Chloro-2-nitroeniline- Orange. 5-Nitr01:2-toluidine Orange.

mean

Shades 4-Niti o-1-na' hthylamlne a-Ammoant aquinone..

Brownish orange. 1

Brownly orsnge.

Ortho;eminoazotoluene.- Orange yellow. 0.o -D1chlorobenzidine Golden-orange.

(Orange.

Meta-nitrobenzene-azometwtoluidine'. Amino-azo-para-cresetol- Para-chlorobenzene-azopara-cresidine. Para-methoxybenzeueazo 1- amino- Z-neph- 4 Reddish orange. Orange red.

Bordeaux.

tholethylether. 4.4 -Diamlnodiphenyldo Brown.

amine. o-Chloroamlme Dlbenzoylacetyl- Greemsh yellow.

*benzidinide. 2.5-Dichloroaniline- Reddish yellow. 5-Chloro-L2-to1uldlne" Canfi'y yellow.

. o. B-Nitl'o-LZJnlnidine Orange. Ortho-uminoazotoluene Do. a-Aminoanthraqninnne do Do. o-Chloroanfljne DibenzoyIacetyl-or- Lemon yellow.

tho-tolldlnide 2.5-Dichloroanilmedo Reddish yellow. 5-Chloro-1.2-to1uidine-- -do Do. tS-Nitro-l.2-toluidlne. "do/(examples) Golden orange. Ortho-aminoazotoluene do Do. a-Amlnoanthrequinone. -..-.do Do.

.....do Reddisl yellow.

2-Chloro-1A-toluidino.-.

Now what we claim and desire-to secure by Letters Patent is the follo 1. As new products the ex soluble in water, whichcan be obtains combining a diazo compound not contamwith a dine ing a sulfo. or

carboxglic diacyl acetyl compoun of series of the general formula:

' rnocnaconnn.

wherein X means a di radical of the hydrocar on genes, dyestuffs probably have the general I formula 2 luv.

l residue, Y any whic to p

t wherein X means a die 1 residue, I an radical of the hydrocar 11. series, whic are when dry yellow to brown and Bordeaux red powders, insoluble .in water; and solusoluble in water consisting in combining a diazo compound not containin a sulfo'or carboxyllc group with a diacy acetyl comp0und-of the benzidme series of the general formula:

Y.CO.CH .CO.LXNHCOEH COY, wherein X means a diaryl residue, Y any radical of the hydrocarbon series .3. A process of producing on the fiber of cotton goods, azodyestufls insoluble in water, which consists in treating the cotton goods after impregnation with a vdiacyl acetyl compound of the benzidineseriesof the general formula: v

Y.CO.CH ;.CO.NH.X;NH.CO,CH .CO.Y, wherein X means a diaryl residue, Yany radical of the hydrocarbon series, with a.

diazo compound not containing a sulfo or carboxylic group.

4. As new products the azodyestu fls, in-

i wherein X means 'a diaryl'residue, which ellow to brown and Borare, insoluble in water, and soluble ,in sulfuric ac'id'to a yellow towiolet solution, said dyestufis yieldin Valuable lakesand, when produced on t e fiber fast yellow to brown and Bordeaux sha es. 1

5%.Aprocess of making azodyestufl s, insoluble in water consisting combining a diazo compound not contalmng a sulfo or carboxylic group with a diacetoacetyl oomare. when dry pound of the'benz idine series of the'general formula ble in sulfuric acid to a yellow to violet soluti'on, saiddyestufis yielding valuable lakes and, when produced on the fiber fast yellow toLbrown and Bordeaux red shades.

LA process of producm I cotton of inon coon ponnxp NH.CO.GH .RCO .OH wherein X means a diarylresidue.

gods, ,azodyest s insoluble in water, iJOhyCOIlBlSlB ill treating the cotton on the fiber of goods after impregnetien efiiaceteacetyl cempouml of the benziine series (ME the general formula:

CH3.CO.CHZ.CQ.NH.X.

- sssess eems formula: Y

CH .CO.CH .CO.NH.X.

NHQQCHQEQGE Whemin X means & ieryl resiclue, which dyestuffs probably have Elle general 50rmula.

CH2 r (EH-JI N-eryl (negatively substituzed} (i0 !IE 5;, is 60 wherein e {lieryl resiue, which 3 sscacs sose when cleauz real ssluhle 1 wherein means a clisryl residue.

precess efproi leing on the fiber of autism gooils, azodlyesfufi's insoluble in Wefer eensisi's in treating the cotton gcmals efier impregnaticm with a disasteacetyl esmpsmd Gillie ben zidine series of the general iarmule:

NEGQCH GQ, wherein Z means a cliaryl residue, with a, cliaze compeumi negatively substituted and net wmsmm a sufie 0r csrboxylic group.

10; sew articles the azoclyestufis, msoluhle water, which can be obtained by eembiming in diam csmpomfi not containing 4 0 e ssfie er carlscwxylie grasp with diac-etol eceqgl-erthe-tolieinicle: J

angstroms-s0 Li H-CQGH -COGE;

V V ers Whisk dgestufi's probs nlg have the general a which are when shades.

eshes 12. A process of producing on the fiber of cotton goods, azodyestufi's insoluble in water, which consists in treating the cotton with a diazo compound not containing a sulfo or carboxylic' oup. e I

13. As new a tic es the azodyestufis, in-

soluble in water, which can be obtained by which dyestufls probably have the general v J which are, when Bordeaux red pow ers insoluble in water, and soluble iii sulfuric acid to 'ayellow to violet' solution, said dyestufis able lakes and when produced on the fiber fast yellow. tobr'own and Bordeaux red yellow to; brown and 11 A process of making azodyestufis, insoluble in water consisting in combining a diazo compound not containing a sulfo or carboxylic tolidine:

group with diacetoacetyl-ortho- NH-cocm-oocm.

goods after impregnation with diacetoacetylortho-tolidine:

Nn-oooHr-oocm combining a diazo compound negatively substituted and notcontaining a sulfo or carboxylic group, with diacetoacetyl-orthotolidine:

formula 2 H-N==Neryl nemawnmmnmma) ,1 dJH-N N-aml (veli substituted) 14; A process oi making azodyestufils, insoluble in water consisting 1n combmmg a diazo compound ne atively substltuted and;

with diacetoacetyl-ortho-tolidine:

, mxooom-coom -not containing a su fo or carboxylic group I which d'yestufi's probably have the 15. A process of producing on the fiber of cotton goods, azodyestufls insoluble in water, which consists in treating the cotton mosses goods after impregnation with diacetylortho-tolidine:

combining a diatzo compound cnloro substituted and not containing a sulfo or carbonylic group, with diacetoacetyl-ortho-tolidine 2 general formula:

which are lwhen dry, yellow to brown and Bordeaux red powders, insoluble in water,'

and soluble in sulfuric acid to a yellow to violet solution, said dyestufl's yielding valuof cotton In testimony whereof we affix our signatures.

able lakes and, when produced on the fiber, fast yellow to brown and Bordeaux red shades.

CH -COOHg-CO-NH v1 H v 18. A process of producing on the oods, azodyestufi's insoluble in Water, whic consists in treating the cotton with a; diezo compound chloro substituted and not containing a; sulfo or carboxylic group.

A 17. A process of melting azodyestufi's, in- 7 soluble in water, consisting in combining a diazo compound chloro substituted and not containing a sulfo or carboxylic group with diacetoacetyl -ortho-tolidine:

-NH-oocnT-cocm om n goods after impregnsting with 'diacetoacetyl-ortho-tolidine:

ARTHUR ZITSOHER.

Witnesses O. C. L.'B.'WYmis,

' AUGUST LEOPOLD LASKA. Q 

